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CN110352183B - 含石墨的耐火物及含石墨的耐火物的制造方法 - Google Patents

含石墨的耐火物及含石墨的耐火物的制造方法 Download PDF

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CN110352183B
CN110352183B CN201880013645.5A CN201880013645A CN110352183B CN 110352183 B CN110352183 B CN 110352183B CN 201880013645 A CN201880013645 A CN 201880013645A CN 110352183 B CN110352183 B CN 110352183B
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containing refractory
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CN110352183A (zh
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吉田圭佑
松永久宏
滨洋一郎
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JFE Steel Corp
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Abstract

本发明提供一种比现有的耐火物的弯曲强度和破坏能量高的含石墨的耐火物及该耐火物的制造方法。所述含石墨的耐火物是石墨的含量为1质量%以上且80质量%以下的范围内的含石墨的耐火物,其中,在内部配置有长度为100mm以上的碳纤维束,所述碳纤维束通过在1000根以上且300000根以下的范围内捆扎碳纤维而形成,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内。

Description

含石墨的耐火物及含石墨的耐火物的制造方法
技术领域
本发明涉及在内部配置有碳纤维束的含石墨的耐火物及含石墨的耐火物的制造方法。
背景技术
在炼钢厂的炼铁工序、炼钢工序中使用的设备(精炼容器、输送容器等)为了耐受高温下长时间的使用而实施了内衬耐火物的施工。精炼工序中使用的转炉使用了氧化镁/碳质耐火物,铁水预处理工序中使用的鱼雷罐、高炉钢包的内衬使用了氧化铝/碳化硅/碳质耐火物。这些耐火物在由装入物导致的机械冲击、由钢水及熔融炉渣的搅拌导致的磨耗、由熔融炉渣导致的炉渣侵蚀及操作中的急剧温度变化等非常严苛的条件下使用。因此,为了进行稳定的操作,优选使用能耐受严苛条件的耐用性高的耐火物。
作为提高耐火物的耐用性的技术,专利文献1中公开了一种耐火物,其用合成树脂等将棒状或网状的高强度纤维束固化并在不破坏高强度纤维束的形状的情况下配置于内部。记载了,通过这样地在不破坏高强度纤维束的形状的情况下配置在耐火物的内部,可以提高耐火物的机械强度和耐剥落性。专利文献2中公开了一种耐火物,其通过耐热性的粘接剂将由拉伸强度高的纤维形成的单向的束、合股线或织物粘接在表面的一部分或整个表面。记载了,通过这样地在表面的一部分或整个表面将由拉伸强度高的纤维形成的单向的束、合股线或织物粘接于耐火物,可以改善拉伸强度,抑制发产生裂纹、破坏,由此能够提高耐火物的寿命。
现有技术文献
专利文献
专利文献1:日本特开2005-320196号公报
专利文献2:日本特开2007-106618号公报
发明内容
发明所要解决的课题
专利文献1及专利文献2中公开的耐火物中配置的碳纤维的长度为90mm以下,存在作为在暴露于严苛条件下的转炉等中使用的耐火物的强度不足的课题。本发明是鉴于上述课题而完成的,其目的在于提供与现有的耐火物相比弯曲强度及用于破坏耐火物所需的能量(以下记载为“破坏能量”)高的含石墨的耐火物、以及含石墨的耐火物的制造方法。
用于解决课题的方法
解决这样的课题的本发明的特征如下所述。
(1)一种含石墨的耐火物,其是石墨的含量为1质量%以上且80质量%以下的范围内的含石墨的耐火物,其中,
在内部配置长度为100mm以上的碳纤维束,
所述碳纤维束通过在1000根以上且300000根以下的范围内捆扎碳纤维而形成,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内。
(2)根据(1)所述的含石墨的耐火物,其中,在1000根以上且60000根以下的范围内捆扎所述碳纤维。
(3)根据(1)或(2)所述的含石墨的耐火物,其中,所述含石墨的耐火物包含氧化镁原料,且其含量为20质量%以上且99质量%以下的范围内。
(4)根据(1)或(2)所述的含石墨的耐火物,其中,所述含石墨的耐火物包含氧化铝原料,且其含量为10质量%以上且95质量%以下的范围内,而且包含1质量%以上的碳化硅原料。
(5)根据(4)所述的含石墨的耐火物,其中,所述含石墨的耐火物还包含二氧化硅原料,且其含量为1质量%以上且50质量%以下的范围内。
(6)根据(1)或(2)所述的含石墨的耐火物,其中,所述含石墨的耐火物包含将使用过的耐火物粉碎而得到的耐火物屑,且其含量为10质量%以上且90质量%以下的范围内。
(7)根据(1)~(6)中任一项所述的含石墨的耐火物,其中,使用选自酚醛树脂、氧化铝溶胶、硅溶胶、沥青及焦油中的1种以上粘接剂来粘接所述碳纤维束。
(8)根据(1)~(6)中任一项所述的含石墨的耐火物,其中,使用选自酚醛树脂、环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化铝溶胶、硅溶胶、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶、氧化钇溶胶、沥青、焦油及淀粉糊中的1种以上粘接剂来粘接所述碳纤维束。
(9)根据(1)~(8)中任一项所述的含石墨的耐火物,所述含石墨的耐火物还额外包含短碳纤维,且其含量相对于所述含石墨的耐火物为0.10质量%以上且10质量%以下的范围内,所述短碳纤维的纤维直径为1μm/根以上且45μm/根以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)为2以上且1000以下。
(10)一种含石墨的耐火物的制造方法,所述含石墨的耐火物在1质量%以上且80质量%以下的范围内含有石墨,且在内部配置有碳纤维束,该方法具有如下工序:
成束工序,将碳纤维捆扎而形成所述碳纤维束;
配合工序,在耐火物原料中配合石墨而制成含石墨的耐火物原料;
成型工序,将配置有所述碳纤维束的所述含石墨的耐火物原料成型而制成成型体;以及
干燥工序,对所述成型体进行干燥,
其中,
在所述成束工序中,在1000根以上且300000根以下的范围内捆扎所述碳纤维,形成长度100mm以上的碳纤维束,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内。
(11)根据(10)所述的含石墨的耐火物的制造方法,其中,在所述成束工序中,在1000根以上且60000根以下的范围内捆扎所述碳纤维。
(12)根据(10)或(11)所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化镁原料,
在所述配合工序中,在20质量%以上且99质量%以下的范围内配合所述氧化镁原料。
(13)根据(10)或(11)所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化铝原料及碳化硅原料,
在所述配合工序中,在10质量%以上且95质量%以下的范围内配合所述氧化铝原料,
配合1质量%以上的所述碳化硅原料。
(14)根据(13)所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化铝原料、碳化硅原料及二氧化硅原料,
在所述配合工序中,在10质量%以上且95质量%以下的范围内配合氧化铝原料,
配合1质量%以上的所述碳化硅原料,
在1质量%以上且50质量%以下的范围内配合所述二氧化硅原料。
(15)根据(10)或(11)所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料是将使用过的耐火物粉碎而得到的耐火物屑,
在所述配合工序中,在10质量%以上且90质量%以下的范围内配合所述耐火物屑。
(16)根据(10)~(15)中任一项所述的含石墨的耐火物的制造方法,其中,
在所述成束工序中,使用选自酚醛树脂、氧化铝溶胶、硅溶胶、沥青及焦油中的1种以上粘接剂来粘接所述碳纤维。
(17)根据(10)~(15)中任一项所述的含石墨的耐火物的制造方法,其中,
在所述成束工序中,使用选自酚醛树脂、环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化铝溶胶、硅溶胶、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶、氧化钇溶胶、沥青、焦油及淀粉糊中的1种以上粘接剂来粘接所述碳纤维。
(18)根据(10)~(17)中任一项所述的含石墨的耐火物的制造方法,其中,
在所述成型工序之前,还具有如下工序:
混炼工序,对所述含石墨的耐火物原料进行混炼;以及
填充工序,在将所述含石墨的耐火物原料成型的模框中填充经混炼的含石墨的耐火物原料和所述碳纤维束。
(19)根据(18)所述的含石墨的耐火物的制造方法,其中,
在所述填充工序中,重复进行在相对于所述模框的容积填充了5容积%以上的所述含石墨的耐火物原料后以相互间隔距离为3mm以上排列配置所述碳纤维束的操作,在所述模框中填充所述含石墨的耐火物原料和所述碳纤维束。
(20)根据(10)~(17)中任一项所述的含石墨的耐火物的制造方法,其中,
在所述成型工序之前,还具有如下工序:
混炼工序,对所述含石墨的耐火物原料进行混炼;以及
填充工序,在将所述含石墨的耐火物原料成型的成型容器中填充经混炼的含石墨的耐火物原料和所述碳纤维束,
在所述成型工序中,通过压力介质对所述成型容器施加压力而成型为成型体。
(21)根据(10)~(20)中任一项所述的含石墨的耐火物的制造方法,其中,
在所述配合工序中,相对于所述含石墨的耐火物原料,额外在0.10质量%以上且10质量%以下的范围内配合短碳纤维,所述短碳纤维的纤维直径为1μm以上且45μm以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)为2以上且1000以下的范围内。
发明的效果
通过在内部配置具有100mm以上的长度的碳纤维束,能够制造与现有相比弯曲强度和破坏能量高的含石墨的耐火物。通过将这样提高了弯曲强度和破坏能量的含石墨的耐火物用于例如转炉耐火物,可以实现稳定的转炉操作,能够延长含石墨的耐火物的寿命。
附图说明
图1是示出本实施方式的氧化镁/碳质耐火物10的一个例子的立体图和侧视图。
图2是碳纤维束14的立体图。
图3是示出将氧化镁/碳质耐火物10用作转炉耐火物的一个例子的立体示意图。
图4是示出垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为45°的氧化镁/碳质耐火物10的立体图和侧视图。
图5是示出垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为135°的氧化镁/碳质耐火物10的立体图和侧视图。
图6是示出本实施方式的氧化镁/碳质耐火物10的制造流程的一个例子的图。
图7是说明基于CIP成型的成型方法的图。
图8是说明使用了高频感应炉50的熔损试验的剖面示意图。
图9示出了利用3点弯曲试验方法得到的载荷-位移曲线的一个例子。
图10是示出实施例9-1~9-3的碳纤维束的装入角度的剖面示意图。
图11是示出利用CIP装置进行成型的状态的剖面示意图。
图12是示出实施例10-1~10-3的碳纤维束的装入角度的剖面示意图。
图13是示出利用CIP装置进行成型的状态的剖面示意图。
符号说明
10 氧化镁/碳质耐火物
12 氧化镁/碳质原料
14 碳纤维束
16 成型面
18 虚线
20 箭头
30 支撑构件
32 芯金属
34 上支撑盘
35 下支撑盘
36 成型容器
38 CIP装置
40 压力介质
50 高频感应炉
52 感应线圈
54 底板
56 铁水
58 合成炉渣
60 含石墨的耐火物
具体实施方式
用于转炉的内衬的氧化镁/碳质耐火物在由装入物导致的机械冲击、由钢水和熔融炉渣的搅拌导致的磨耗、由熔融炉渣导致的炉渣侵蚀及转炉操作中的急剧温度变化等非常严苛的条件下使用。因此,为了进行稳定的操作,优选使用耐受这样的严苛条件的耐用性高的氧化镁/碳质耐火物。同样地,用于鱼雷罐、高炉钢包等铁水预处理容器的内衬的氧化铝/碳化硅/碳质耐火物也在非常严苛的条件下使用,因此优选使用耐受这些条件的耐用性高的氧化铝/碳化硅/碳质耐火物。
本发明人等发现,通过将长度为100mm以上的碳纤维束配置在耐火物的内部,所述碳纤维束在1000根以上且300000根以下的范围内捆扎碳纤维而形成,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内,与现有相比,含石墨的耐火物的弯曲强度和破坏能量增高,从而完成了本发明。以下,使用氧化镁/碳质耐火物的例子作为本发明的实施方式对本发明进行说明。
图1是示出本实施方式的氧化镁/碳质耐火物10的一个例子的立体图和侧视图。图1(a)是氧化镁/碳质耐火物10的立体图,图1(b)是氧化镁/碳质耐火物10的侧视图。在本实施方式的氧化镁/碳质耐火物10中,在石墨中配合有氧化镁原料的氧化镁/碳质原料12的内部,沿着长边方向配置有多个碳纤维束14。由此,使氧化镁/碳质耐火物10的弯曲强度和破坏能量增高。
在本实施方式的氧化镁/碳质耐火物10中,在1质量%以上且80质量%以下的范围内包含石墨,在20质量%以上且99质量%以下的范围内包含氧化镁原料。由此,能够抑制由热剥落导致的耐火物破裂,且能够提高对转炉炉渣的耐熔损性。另一方面,将石墨的含量设为低于1质量%时,无法抑制由热剥落导致的耐火物破裂,耐破裂性大幅降低。将氧化镁原料的含量设为低于20质量%时,对转炉炉渣的耐熔损性降低,熔损量增大。
图2是碳纤维束14的立体图。碳纤维束14通过捆扎多个碳纤维而形成。碳纤维束14的长度L1为100mm以上,且设为沿着配置有碳纤维束14的氧化镁/碳质耐火物10中的碳纤维束14的长度方向的长度以下。对于碳纤维束14而言,在1000根以上且300000根以下的范围内捆扎纤维直径为1μm/根以上且45μm/根以下的范围内的碳纤维,使得端面的宽度L2为1.0mm以上且20.0mm以下、厚度L3为0.001mm以上且6.0mm以下、L2的长度大于L3。
由此,本实施方式中,碳纤维束14通过在1000根以上且300000根以下的范围内捆扎碳纤维而形成,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内。由此,在配置有碳纤维束14的部位表现出通过碳纤维束14抑制裂纹发展的效果,氧化镁/碳质耐火物10的弯曲强度和破坏能量增高。另一方面,在制成碳纤维的纤维直径低于1μm/根且根数低于1000根的碳纤维束时,由于碳纤维束过细,因此碳纤维束无法抑制裂纹的发展,不能提高弯曲强度和破坏能量。在制成碳纤维的纤维直径超过45μm/根且根数超过300000根的碳纤维束时,由于碳纤维束过粗,因此碳纤维束与耐火物原料的抱合变差,成型时发生回弹,变得难以成型。还可以通过在1000根以上且60000根以下的范围内捆扎碳纤维而形成碳纤维束14。
碳纤维束14优选将上述碳纤维的束涂有选自以下的1种以上粘接剂来进行粘接:酚醛树脂、环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化铝溶胶、硅溶胶、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶、氧化钇溶胶、沥青、焦油及淀粉糊。通过粘接碳纤维的束,从而使碳纤维之间的密合性及碳纤维束与耐火物原料的密合性提高、使成型体更致密化,因此氧化镁/碳质耐火物10的弯曲强度和破坏能量增高。
碳纤维束14的端面宽度L2的长度大于端面厚度L3。通过这样地制成碳纤维束14的端面宽度L2的长度大于端面厚度L3的扁平形状,能够对碳纤维束14赋予弯曲强度的各向异性。此外,通过使如此赋予了弯曲强度的各向异性的碳纤维束14的朝向对齐地配置于耐火物的内部,可使氧化镁/碳质耐火物10也具有弯曲强度的各向异性。
本实施方式的氧化镁/碳质耐火物10是从与成型面16垂直的方向进行压制、成型而制造的耐火物。如图1所示,碳纤维束14以如下方式配置:将碳纤维束14的端面的长边方向的朝向沿同一方向对齐,且使成型面16与端面长边方向的角度θ1为90°。在图1(b)中,虚线18是为了表示成型面16与碳纤维束14的端面长边方向的角度θ1而绘制的与成型面16平行的线。
通过这样地以端面长边方向与成型面16的角度θ1为90°的方式将碳纤维束14的端面宽度方向的朝向沿同一方向对齐进行配置,在进行成型的压制时,氧化镁/碳质原料12易于进入碳纤维束14的周围,氧化镁/碳质耐火物10的成型性提高。另外,通过将长度方向的朝向沿同一方向对齐进行配置,氧化镁/碳质耐火物10也具有弯曲强度的各向异性,通过以长边方向与成型面16的角度θ1为90°的方式配置碳纤维束14,与作为氧化镁/碳质耐火物10的碳纤维束14的端面短边方向的方向的弯曲强度相比,能够提高作为碳纤维束14的端面长边方向的方向的弯曲强度。长边方向与成型面16的角度θ1优选设为90°,以施工上的精度而言,90±45°左右的误差是可以接受的。
图3是示出将氧化镁/碳质耐火物10用作转炉耐火物的一个例子的立体示意图。如图3所示,在转炉中使用了氧化镁/碳质耐火物10的情况下,氧化镁/碳质耐火物10设置成使成型面16朝向转炉的圆周方向(图3中,箭头20)上。在该情况下,由于转炉操作中的急剧温度变化而使氧化镁/碳质耐火物10反复发生膨胀和收缩,由此在圆周方向、即与成型面16垂直的方向上产生应力。
如上所述,本实施方式的氧化镁/碳质耐火物10具有弯曲强度的各向异性,与成型面16垂直的方向的弯曲强度高于与成型面16平行的方向的弯曲强度。因此,通过将氧化镁/碳质耐火物10的成型面16朝向转炉中产生应力的圆周方向进行配置,可制成能够对在转炉中产生的应力表现出高弯曲强度的氧化镁/碳质耐火物10。通过这样地将具有弯曲强度各向异性的本实施方式的氧化镁/碳质耐火物10的弯曲强度高的方向朝向转炉中产生应力的方向进行配置,能够提高氧化镁/碳质耐火物10的耐用性。
如图1所示,本实施方式的氧化镁/碳质耐火物10以如下方式配置:垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为90°。通过这样地配置碳纤维束14,与以垂直于成型面16的方向和沿碳纤维束14的长度L1的方向平行的方式进行配置的情况相比,氧化镁/碳质耐火物10对于垂直于成型面16的方向的力的弯曲强度和破坏能量增高。
图4是示出垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为45°的氧化镁/碳质耐火物10的立体图和侧视图。图5是示出垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为135°的氧化镁/碳质耐火物10的立体图和侧视图。如图4和图5所示,优选以使垂直于氧化镁/碳质耐火物10的成型面16的方向与沿碳纤维束14的长度L1的方向的角度θ2为45°以上且135°以下的范围内的方式配置碳纤维束14。由此,与以垂直于氧化镁/碳质耐火物10的成型面16的方向和沿碳纤维束14的长度L1的方向平行的方式配置了碳纤维束14的情况相比,可以提高氧化镁/碳质耐火物10的弯曲强度和破坏能量。图4、图5中示出了使各碳纤维束14平行且与面AEHD平行地进行配置时的例子,但只要角度θ1和θ2分别为45°以上且135°以下的范围内,即使各碳纤维束14不平行,氧化镁/碳质耐火物10的弯曲强度和破坏能量也增高。
本实施方式的氧化镁/碳质耐火物10还额外包含短碳纤维,且其含量相对于氧化镁/碳质原料12为0.10质量%以上且10质量%以下的范围内,所述短碳纤维的纤维直径为1μm/根以上且45μm/根以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)在2以上且1000以下的范围内。通过包含短碳纤维,该短碳纤维抑制氧化镁/碳质耐火物10的裂纹的发展,由此使氧化镁/碳质耐火物10的弯曲强度和破坏能量增高。
图6是示出本实施方式的氧化镁/碳质耐火物10的制造流程的一个例子的图。使用图6对氧化镁/碳质耐火物10的制造方法进行说明。氧化镁/碳质耐火物10通过碳纤维的成束工序、氧化镁/碳质原料12的配合工序、氧化镁/碳质原料12的混炼工序、填充工序、成型工序和干燥工序来制造。
在碳纤维的成束工序(S101)中,首先,解开例如碳纤维的纤维直径为1μm/根以上且45μm以下的市售的布状的碳纤维,取出长度为100mm以上的丝状的碳纤维。作为市售的碳纤维,有长丝状、丝束状、交叉状等各种形状的碳纤维,可以适当使用任意碳纤维。接着,在1000根以上且300000根以下的范围内捆扎取出的丝状的碳纤维,制成长度为100mm以上的碳纤维束。接着,将碳纤维束在酚醛树脂等粘接剂中浸渍1~2分钟左右。从酚醛树脂等粘接剂中取出碳纤维束,进行24小时以上的自然干燥。
在氧化镁/碳质原料12的配合工序(S102)中,以石墨的含量相对于氧化镁/碳质原料12为1质量%以上且80质量%以下、氧化镁原料的含量相对于氧化镁/碳质原料12为20质量%以上且99质量%以下的方式进行配合,制成氧化镁/碳质原料12。进而,在配合工序中额外添加给定量的固化剂及粘合剂。
在配合工序中,除了石墨以外,还可以在氧化镁/碳质原料12中配合短碳纤维,所述短碳纤维的纤维直径为1μm以上且45μm以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)在2以上且1000以下的范围内。
在氧化镁/碳质原料12的混炼工序(S103)中,使用混炼装置对氧化镁/碳质原料12进行混炼。在填充工序(S104)中,相对于耐火物的模框的容积填充5容积%以上的经混炼的氧化镁/碳质原料12,然后,排列配置碳纤维束14,使得碳纤维束14的相互间隔距离为3mm以上。接着,相对于模框的容积填充5容积%以上的经混炼的氧化镁/碳质原料12,然后,排列配置碳纤维束14,使得碳纤维束14的相互间隔距离为3mm以上。重复实施该氧化镁/碳质原料12的填充和碳纤维束14的配置,在模框中填充氧化镁/碳质原料12和碳纤维束14。
通过这样地排列配置碳纤维束14,使得碳纤维束14的相互间隔距离为3mm以上,并且交替重复氧化镁/碳质原料12的填充和碳纤维束的配置,使碳纤维在横向和高度方向上分散而配置,能够增加氧化镁/碳质原料12与碳纤维束的接触面积,由此,氧化镁/碳质耐火物的弯曲强度和破坏能量增高。另一方面,在未使碳纤维束在横向和高度方向上分散而配置的情况下,无法增加氧化镁/碳质原料12与碳纤维束的接触面积,不能提高氧化镁/碳质耐火物10的弯曲强度和破坏能量。优选以碳纤维束14的相互间隔距离为100mm以下的方式进行配置。碳纤维束14的相互间隔距离超过100mm时,碳纤维束14变少,提高弯曲强度和破坏能量效果减小。
优选在混炼工序中实施了氧化镁/碳质原料12的混炼后,在填充工序中在经混炼的氧化镁/碳质原料12中配置碳纤维束14。在配置碳纤维束14后实施混炼工序时,因设置于混炼机的搅拌叶片而将碳纤维束14切断,使提高氧化镁/碳质耐火物的弯曲强度和破坏能量的效果减小,因此不优选。
在成型工序(S105)中,从与成型面16垂直的方向进行压制,将模框的内部形状转印至填充于耐火物的模框内的氧化镁/碳质原料12,将成型体成型。作为模框,可以使用金属、木材、合成树脂、橡胶等材质的模框。成型体在干燥工序(S106)中以230℃进行18小时干燥,制造在内部配置有碳纤维束14的氧化镁/碳质耐火物10。
在本实施方式中,示出了使用氧化镁原料作为耐火物原料的例子,但并不限定于此,也可以使用氧化铝原料和碳化硅原料来代替氧化镁原料,还可以使用氧化铝原料、碳化硅原料及二氧化硅原料。在使用了氧化铝原料和碳化硅原料的情况下,只要在相对于含石墨的耐火物原料为10质量%以上且95质量%以下的范围内配合氧化铝原料、且配合相对于含石墨的耐火物原料为1质量%以上的碳化硅原料即可。在使用了氧化铝原料、碳化硅原料及二氧化硅原料的情况下,只要在相对于含石墨的耐火物原料为10质量%以上且95质量%以下的范围内配合氧化铝原料、配合相对于含石墨的耐火物原料为1质量%以上的碳化硅原料、且在相对于含石墨的耐火物原料为1质量%以上且50质量%以下的范围内配合二氧化硅原料即可。
通过将氧化铝原料的配合量设为10质量%以上且95质量%以下,不仅能够提高对铁水预处理炉渣的耐熔损性,而且可以抑制因热剥落导致的破裂。另一方面,将氧化铝原料的配合量设为低于10质量%时,对铁水预处理炉渣的耐熔损性降低,因此不优选。将氧化铝原料的配合量设为超过95质量%时,无法抑制因热剥落导致产生裂纹,耐破裂性降低,因此不优选。
通过将碳化硅原料的配合量设为1质量%以上,能够抑制在大气氛围下的石墨的氧化,因此能够保持含石墨的耐火物的高耐破裂性。另一方面,将碳化硅原料的配合量设为低于1质量%时,无法抑制大气氛围下的石墨的氧化,含石墨的耐火物的耐破裂性降低,因此不优选。
通过将二氧化硅原料的配合量设为1质量%以上且50质量%以下,可以制成兼顾高耐破裂性和高耐熔损性的含石墨的耐火物。另一方面,将二氧化硅原料的配合量设为低于1质量%时,膨胀量小,不会产生微细裂纹,因此无法增加耐热冲击断裂性,耐破裂性降低,因此不优选。将二氧化硅原料的配合量设为超过50质量%时,耐熔损性大幅降低,因此不优选。
通过这样地在石墨中如上所述地配合氧化铝原料和碳化硅原料、或者氧化铝原料、碳化硅原料及二氧化硅原料,能够提高含石墨的耐火物对铁水预处理炉渣的耐熔损性,且可以提高含石墨的耐火物的弯曲强度和破坏能量。因此,该耐火物可以优选用作鱼雷罐、高炉钢包等铁水预处理容器的内衬耐火物。
在本实施方式中示出了使用氧化镁原料作为耐火物原料的例子,但并不限定于此,还可以使用氧化铝原料和氧化锆原料来代替氧化镁原料。对于包含氧化铝原料、氧化锆原料及石墨的板耐火物而言,也可以通过配置本实施方式的碳纤维束来提高该板耐火物的弯曲强度和破坏能量。
在本实施方式中示出了使用氧化镁原料作为耐火物原料的例子,但并不限定于此,还可以使用将使用过的氧化铝/碳化硅/碳质耐火物粉碎而得到的耐火物屑来代替氧化镁原料。在使用了耐火物屑的情况下,只要在相对于含石墨的耐火物原料为10质量%以上且90质量%以下的范围内配合耐火物屑即可。由此,能够实现与仅使用了尚未使用的初始原料时的含石墨的耐火物同等程度的耐破裂性和耐熔损性。
使用了耐火物屑的耐火物屑原料比初始原料的纯度低,但通过在耐火物屑中配合10质量%以上的初始原料,可以抑制耐火物原料中具有的Al2O3成分所具有的耐熔损性的大幅降低。另一方面,将耐火物屑原料的配合量设为超过90质量%时,初始原料的配合量变得过少,无法抑制耐火物屑原料中具有的Al2O3成分所具有的耐熔损性的大幅降低。将耐火物屑原料的配合量设为低于10质量%时,由于耐火物屑的再利用率过低,因此作为工业废料的耐火物屑的处理费用大幅增加。
本实施方式中示出了在模框中填充含石墨的耐火物原料和碳纤维束14并将成型体成型的例子,但并不限定于此。例如,还可以通过使用了如图7所示那样的成型容器的CIP成型将成型体成型。图7是说明基于CIP成型的成型方法的图,图7(a)示出了在成型容器36中填充了氧化镁/碳质原料12和碳纤维束14的状态,图7(b)示出了将成型容器36装入充满压力介质40的CIP装置38中的状态。
首先,对在成型容器36中填充氧化镁/碳质原料12和碳纤维束14的方法进行说明。在具有芯金属(core metal)32、上支撑盘34和下支撑盘35的支撑构件30中,以与芯金属32平行的方式将多个碳纤维束14架设于上支撑盘34及下支撑盘35进行配置。将架设有碳纤维束14的支撑构件30配置在橡胶制的成型容器36内。在由支撑构件30和成型容器36形成的空间区域填充氧化镁/碳质原料12,关闭成型容器36的开口进行密闭。将密封后的成型容器36装入被例如水、油等压力介质40充满的CIP装置38中,对压力介质40施加49MPa以上且490MPa以下的压力。由此,可以通过压力介质40对成型容器36施加均等的压力,能够将成型体成型。CIP成型优选用于大风口耐火物的成型,芯金属32的长度、芯金属32的直径、上支撑盘34、下支撑盘35的大小、成型容器36的大小可以根据希望的风口耐火物的风口直径等的大小而适当确定。在进行CIP成型时,成型容器36的材质优选使用橡胶。
实施例
接着,对实施例进行说明。通过以下所示的方法对以转炉中使用的氧化镁/碳质原料作为骨料的含石墨的耐火物进行了评价。首先,为了研究氧化镁原料和石墨的含量,如表1所示,改变氧化镁原料的含量和石墨的含量,依据图6的流程,制作了含石墨的耐火物,然后对耐熔损性和耐破裂性进行了评价。
Figure GDA0002177168210000151
对于耐熔损性,利用图8所示的使用了高频感应炉的内衬分隔法来进行测定。
图8是说明使用了高频感应炉50的熔损试验的剖面示意图。如图8所示,将含石墨的耐火物60以筒状设置在具备感应线圈52的高频感应炉50的底板54上,试验温度为1500℃,将温度保持时间设为4小时,每1小时投入铁水56或表2所示的组成的合成炉渣58,在冷却后测定了熔损量。以将实施配合例1-3的熔损量设为100的熔损指数评价了表1的耐熔损性。即,在熔损指数低于100时,表明熔损量少于实施配合例1-3,在熔损指数超过100时,表明熔损量多于实施配合例1-3。
[表2]
Figure GDA0002177168210000161
对于耐破裂性,按照JIS(日本工业标准)R 1605中规定的超声波脉冲法测定了40×40×200mm的试样的长度方向的动态弹性模量(dynamic elastic modulus)E0。将以1500℃加热10分钟、水冷5分钟、大气冷却10分钟作为一次循环的剥落试验重复实施3次,然后,再次测定动态弹性模量E3,计算出试验前后的动态弹性模量的变化率E3/E0,利用该值评价了耐破裂性。该动态弹性模量的变化率E3/E0小表明耐破裂性低。
如表1所示,将石墨的含量设为1质量%以上且80质量%以下、且将氧化镁原料的含量设为20质量%以上且99质量的实施配合例1-2~1-8的耐熔损性、耐破裂性是恒定的,但将石墨的含量设为0.5质量%的实施配合例1-1的耐破裂性大幅降低,将氧化镁原料的含量设为10.0质量%的实施配合例1-9的耐熔损性大幅降低。根据这些结果可以确认,在使用了氧化镁原料作为耐火物原料的情况下,通过将石墨含量设为1质量%以上且80质量%以下、且将氧化镁原料的含量设为20质量%以上且99质量%以下,能够兼顾含石墨的耐火物的耐熔损性和耐破裂性。
接下来,对于碳纤维束的长度对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表3。
Figure GDA0002177168210000171
如表3所示,在以使碳纤维束14的端面为扁平形状的方式捆扎了990~12000根纤维直径为0.8~7μm/根的碳纤维时,碳纤维束14的端面的宽度尺寸为1.0mm以上且20.0mm以下的范围内,厚度为0.001mm以上且10.0mm以下的范围内。碳纤维使用了将TorayIndustries公司制造的TORAYCA(注册商标)型号CK6261C开纤而得到的纤维。将该碳纤维束分别切成90mm、100mm、200mm、400mm、600mm、800mm、1000mm的长度,为了使碳纤维之间的密合性及碳纤维束与氧化镁/碳质原料的密合性提高,将碳纤维束在酚醛树脂中浸渍1分钟而使其密合,然后,通过以下的方法填充了这些碳纤维束和氧化镁/碳质原料。
相对于耐火物的大小为长边方向1000mm、短边方向300mm、高度90mm的模框的模框容积,在模框的底部填充10容积%的氧化镁/碳质原料,以垂直于成型面的方向与沿碳纤维束的长度L1的方向的角度θ2为90°、且碳纤维束的相互间隔距离为5mm的方式进行配置。填充于模框的氧化镁/碳质原料为表1所示的实施配合例1-5的氧化镁/碳质原料。
通过重复进行该氧化镁/碳质原料的填充和碳纤维束的配置,将氧化镁/碳质原料和碳纤维束填充于模框。在填充结束后,依据图6的流程进行成型、干燥,制作了实施例2~1~2-7及比较例2-1的含石墨的耐火物。测定了该含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
含石墨的耐火物的弯曲强度按照JIS(日本工业标准)R 2213中记载的3点弯曲试验方法来进行,在该方法中,将试验片尺寸设为40×40×140mm,将中心间距离设为100mm,将施加载荷速度设为0.5mm/分。
图9示出了利用3点弯曲试验方法得到的载荷-位移曲线的一个例子。破坏能量可以使用由3点弯曲试验方法得到的载荷-位移曲线进行计算而求出。在载荷-位移曲线上,将表示第1峰值的位移作为基准位置,计算出距该基准位置的位移为1mm范围的面积作为破坏能量。
如表3所示,装入了长度为100mm以上的碳纤维束的实施例2-1~2-7的含石墨的耐火物的弯曲强度和破坏能量显著增高。另一方面,使用了长度低于100mm的碳纤维束的比较例2-1的含石墨的耐火物的弯曲强度和破坏能量低于实施例2-1~2-7的含石墨的耐火物。作为其原因,可以认为是由于比较例2-1的含石墨的耐火物的碳纤维束的长度短,因此未能发挥出碳纤维束带来的抑制耐火物裂纹扩展的效果。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,只要将碳纤维的长度设为100mm以上即可。
接下来,对于碳纤维直径及碳纤维束的根数对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表4。
Figure GDA0002177168210000201
如表4所示,实施例3-1~3-5和比较例3-1、3-2的含石墨的耐火物是在含石墨的耐火物中配置有将碳纤维的捆扎根数设为900根、1000根、10000根、12000根、30000根、60000根、300000根、400000根的碳纤维束而成的含石墨的耐火物,所述碳纤维的长度为600mm、且纤维直径为1μm/根、7μm/根、23μm/根、45μm/根、50μm/根。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同。测定了实施例3-1~3-5和比较例3-1、3-2的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表4所示,使用了将根数为1000根以上且300000根以下的范围内的纤维直径为1μm/根以上且45μm/根以下的范围内的碳纤维捆扎而成的碳纤维束的实施例3-1~3-5及实施例2-5的含石墨的耐火物的弯曲强度和破坏能量高。另一方面,使用了纤维直径低于1μm/根且碳纤维的根数低于1000根的碳纤维束的比较例3-1的含石墨的耐火物的弯曲强度和破坏能量低于实施例2-5及实施例3-1~3-5的含石墨的耐火物。使用了将400000根(超过300000根)的纤维直径50μm/根(超过45μm/根)的碳纤维捆扎而成的碳纤维束的比较例3-2的含石墨的耐火物在成型时发生起层(lamination),碳纤维束从耐火物的侧面露出而难以成型。作为其原因,可以认为是由于碳纤维束过粗,碳纤维束与氧化镁/碳质原料未抱合,在成型时发生了由碳纤维束引起的回弹。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,只要使用将根数为1000根以上且300000根以下的范围内的纤维直径为1μm/根以上且45μm/根以下的范围内的碳纤维捆扎而成的碳纤维束即可。
接下来,对于碳纤维束是否粘接对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表5。
Figure GDA0002177168210000221
如表5所示,实施例4-1~4-11的含石墨的耐火物是配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物,所述碳纤维束是使用酚醛树脂、氧化铝溶胶、二氧化硅溶胶、沥青、焦油及淀粉糊作为粘接剂进行了粘接的碳纤维束、以及未进行粘接的碳纤维束。这些含石墨的耐火物的原料成分与实施配合例1-5相同,大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例4-1~4-11的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表5所示,使用了利用酚醛树脂、氧化铝溶胶、二氧化硅溶胶、沥青、焦油、淀粉糊进行粘接而成的碳纤维束的实施例2-5、4-1~4-5的含石墨的耐火物的弯曲强度和破坏能量高。使用了利用酚醛树脂与氧化铝溶胶、酚醛树脂与硅溶胶、酚醛树脂与沥青、酚醛树脂与焦油、酚醛树脂与淀粉糊进行粘接而成的碳纤维束的实施例4-6~4-10的含石墨的耐火物的弯曲强度和破坏能量高。
另一方面,使用了未进行粘接的碳纤维束的实施例4-11的含石墨的耐火物的弯曲强度和破坏能量低于实施例2-5及实施例4-1~4-10的含石墨的耐火物。作为其原因,可以认为是由于通过粘接碳纤维束,使碳纤维之间的密合性及碳纤维束与氧化镁/碳质原料的密合性进一步提高。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选使用选自酚醛树脂、氧化铝溶胶、硅溶胶、沥青、焦油及淀粉糊中的1种以上粘接剂来粘接碳纤维而制成碳纤维束。另外,可以认为使用与上述粘接剂类似的环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶及氧化钇溶胶,也可以获得同样的效果。
接下来,对于碳纤维束的倾斜程度对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表6。
[表6]
Figure GDA0002177168210000241
如表6所示,实施例5-1~5-3的含石墨的耐火物是将碳纤维束以与耐火物的短边方向的角度θ2为0°、45°、90°、135°的方式配置的含石墨的耐火物,所述碳纤维束是将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。
以与耐火物的短边方向的角度θ2为90°的方式配置有碳纤维束的含石墨的耐火物是图1所示的含石墨的耐火物,以该角度θ2为45°的方式配置的含石墨的耐火物是图4所示的含石墨的耐火物,以该角度θ2为135°的方式配置的含石墨的耐火物是图5所示的含石墨的耐火物。测定了实施例5-1~5-3的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表6所示,以与短边方向的角度θ2为90°的方式配置有碳纤维束的实施例2-5的含石墨的耐火物、以与短边方向的角度θ2为45°的方式配置有碳纤维束的实施例5-1的含石墨的耐火物、以及以与短边方向的角度θ2为135°的方式配置有碳纤维束的实施例5-2的含石墨的耐火物的弯曲强度和破坏能量高。另一方面,以与短边方向的角度θ2为0°的方式配置有碳纤维束的实施例5-3的含石墨的耐火物的弯曲强度和破坏能量低于实施例2-5及实施例5-1、5-2的含石墨的耐火物。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选以与含石墨的耐火物的短边方向的角度θ2为45°以上且135°以下的方式配置碳纤维束。
接下来,对于碳纤维束的间隔对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表7。
[表7]
Figure GDA0002177168210000251
如表7所示,实施例6-1~6-4的含石墨的耐火物是以碳纤维束的相互间隔距离为1mm、3mm、30mm、100mm的方式配置有碳纤维束的含石墨的耐火物,所述碳纤维束是将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例6-1~6-4的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表7所示,以碳纤维束的相互间隔距离为3mm、30mm的方式配置有碳纤维束的实施例6-1、6-2的含石墨的耐火物的弯曲强度和破坏能量稍高于以碳纤维束的相互间隔距离为100mm的方式配置的实施例6-3的含石墨的耐火物的弯曲强度和破坏能量。将碳纤维束的相互间隔距离设为1mm进行配置的实施例6-4的含石墨的耐火物的碳纤维束间隔过小,在成型时容易发生起层(lamination)。因此,实施例6-4的含石墨的耐火物的弯曲强度和破坏能量降低,耐熔损性和耐剥落性也降低。将碳纤维束的相互间隔距离设为100m时的弯曲强度和破坏能量与将碳纤维束的相互间隔距离设为3mm以上且30mm以下的情况相比,虽然稍有降低,但基本上未发生变化。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选将碳纤维束的相互间隔距离设为3mm以上且100mm以下,更优选将碳纤维束的相互间隔距离设为3mm以上且30mm以下。
接下来,对于成型方向上碳纤维束的间隔对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表8。
[表8]
Figure GDA0002177168210000261
如表8所示,实施例7-1的含石墨的耐火物没有重复实施氧化镁/碳质原料的填充和碳纤维束的配置,是将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束配置为一层的含石墨的耐火物。该含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同。测定了该含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表8所示,将碳纤维束配置成层状的实施例2-5的含石墨的耐火物的弯曲强度和破坏能量高。另一方面,将碳纤维束配置成一层的实施例7-1的含石墨的耐火物的弯曲强度和破坏能量低。根据该结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选重复进行氧化镁/碳质原料的填充和碳纤维束的配置,将碳纤维束配置成层状。
接下来,对于碳纤维束的配置时机对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表9。
[表9]
Figure GDA0002177168210000271
如表9所示,实施例8-1的含石墨的耐火物是将碳纤维束配置在混炼后的氧化镁/碳质原料中而制作的含石墨的耐火物,所述碳纤维束是将24000根长度为1200mm、直径为7μm/根的碳纤维捆扎而成的。实施例8-2的含石墨的耐火物是将相同的碳纤维束配置在混炼前的氧化镁/碳质原料中,然后进行混炼而制作的含石墨的耐火物。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同。测定了实施例8-1、8-2的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表9所示,在混炼后的氧化镁/碳质原料中配置有碳纤维束的实施例8-1的含石墨的耐火物的弯曲强度和破坏能量高。另一方面,在混炼前配合碳纤维束后进行混炼的实施例8-2的含石墨的耐火物的弯曲强度和破坏能量低于实施例8-1的含石墨的耐火物。作为其原因,可以认为是由于在配置碳纤维束后进行混炼时,该混炼中碳纤维束被搅拌叶片切断,纤维长度变短,其结果是抑制碳纤维束裂纹扩展的效果降低。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选在混炼耐火物原料后且实施成型工序之前将碳纤维束配置在耐火物原料中。
接下来,对于碳纤维束相对于短边方向的角度对通过CIP成型而制造的含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表10。
[表10]
Figure GDA0002177168210000281
图10是示出实施例9-1~9-3的碳纤维束的装入角度的剖面示意图。如表10和图10(a)、(b)、(c)所示,在支撑构件30中于上支撑盘34与下支撑盘35之间配置将2400根纤维长度800mm、径7μm/根的碳纤维捆扎而成、并利用与表3的说明中记载的粘接方法相同的方法进行了粘接的碳纤维束,使得碳纤维束的长度方向与含石墨的耐火物的短边方向形成的角度θ3为45°(图10(b))、90°(图10(a))、135°(图10(c))及5°、且碳纤维束的相互间隔距离为5mm。将配置有碳纤维束14的支撑构件30放入成型容器36中,将氧化镁/碳质原料12填充至由支撑构件30和成型容器36形成的空间,然后,关闭开口进行密闭。
图11是示出利用CIP装置进行成型的状态的剖面示意图。如图11所示,将密闭的成型容器36装入被压力介质40充满的CIP装置38,通过压力介质40对成型容器36加压。在施加给定时间的压力后,从成型容器36中取出成型体,制作了实施例9-1~9-4的含石墨的耐火物。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同。测定了实施例9-1~9-4的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表10所示,对于将相对于含石墨的耐火物的短边方向的角度θ3设为45°、90°、135°的实施例9-1~9-3的含石墨的耐火物而言,相对于短边方向的应力的弯曲强度和破坏能量高。另一方面,对于将相对于含石墨的耐火物的短边方向的角度θ3设为5°的实施例9-4的含石墨的耐火物而言,相对于短边方向的应力的弯曲强度和破坏能量低于实施例9-1~9-3的含石墨的耐火物。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,在通过CIP成型进行成型而成的含石墨的耐火物中,优选以相对于含石墨的耐火物的短边方向的角度θ3为45°以上且135°以下的方式配置碳纤维束。
对于图10所示的含石墨的耐火物,将碳纤维束的配置方向变更为沿含石墨的耐火物的长度方向的方向,通过CIP成型制造了含石墨的耐火物,对于碳纤维束相对于长边方向的角度对该含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表11。
[表11]
Figure GDA0002177168210000291
图12是示出实施例10-1~10-3的碳纤维束的装入角度的剖面示意图。使用长边方向1500mm、短边方向150mm、高度150mm的成型容器,如表11和图12(a)、(b)、(c)所示,在上支撑盘34与下支撑盘35之间配置将24000根纤维长度1200mm、直径7μm/根的碳纤维捆扎而成、并利用与表3的说明中记载的粘接方法相同的方法进行了粘接的碳纤维束,使得碳纤维束的长度方向与含石墨的耐火物的长边方向形成的角度θ4为45°(图12(b))、90°(图12(a))、135°(图12(c))及5°、且碳纤维束的相互间隔距离为5mm。在将这样配置了碳纤维束14的支撑构件30旋转90°的状态下放入成型容器36中,将氧化镁/碳质原料12填充至由支撑构件30和成型容器36形成的空间,然后,关闭开口进行密闭。
图13是示出利用CIP装置进行成型的状态的剖面示意图。如图13所示,将密闭的成型容器36装入被压力介质40充满的CIP装置38,通过压力介质40对成型容器36加压。在施加给定时间的压力后,从成型容器36中取出成型体,制作了实施例10-1~10-4的含石墨的耐火物。这些含石墨的耐火物的原料成分与实施配合例1-5相同,含石墨的耐火物的大小与实施例2-1相同。测定了实施例10-1~10-4的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表11所示,对于将相对于含石墨的耐火物的长边方向的角度θ4设为45°、90°、135°的实施例10-1~10-3的含石墨的耐火物而言,相对于长度方向的应力的弯曲强度和破坏能量高。另一方面,对于将相对于含石墨的耐火物的长边方向的角度θ4设为5°的实施例10-4的含石墨的耐火物而言,相对于长边方向的应力的弯曲强度和破坏能量低于实施例10-1~10-3的含石墨的耐火物。根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选以相对于含石墨的耐火物的长边方向的角度θ4为45°以上且135°以下的方式配置碳纤维束14。
接下来,对于铁水预处理容器的内衬耐火物中使用的氧化铝原料、碳化硅原料及二氧化硅原料的配合量对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表12。
Figure GDA0002177168210000311
如表12所示,实施例11-1~11-11的含石墨的耐火物是使用变更了氧化铝原料、碳化硅原料、二氧化硅原料及石墨的配合量的含石墨的耐火物原料、且配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物。这些含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例11-1~11-11的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表12所示,将氧化铝原料的配合量设为10质量%以上且95质量%以下的范围内、将二氧化硅原料的配合量设为1质量%以上且50质量%以下的范围内、将碳化硅原料的配合量设为1质量%以上的实施例11-3~11-5及实施例11-7~11-10的含石墨的耐火物的破坏能量高,能够兼顾高耐破裂性和高耐熔损性。另一方面,将氧化铝原料的配合量设为9.0质量%、将二氧化硅原料的配合量设为0.6质量%的实施例11-1的含石墨的耐火物的弯曲强度和耐熔损性降低。将二氧化硅原料的配合量设为0.6质量%的实施例11-2的含石墨的耐火物的耐熔损性降低。将二氧化硅原料的配合量设为55.0质量%的实施例11-6的含石墨的耐火物的耐熔损性也降低。此外,将氧化铝原料的配合量设为99.0质量%的实施例11-11的含石墨的耐火物的弯曲强度和破坏能量降低。根据这些结果可以确认,作为含石墨的耐火物原料,在使用了氧化铝原料、碳化硅原料、二氧化硅原料及石墨的情况下,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选将氧化铝原料的配合量设为10质量%以上且95质量%以下的范围内、将碳化硅原料的配合量设为1质量%以上、将二氧化硅原料的配合量设为1质量%以上且50质量%以下的范围内。
接下来,对于将用于铁水预处理容器的内衬耐火物的使用过的氧化铝/碳化硅/碳质耐火物屑粉碎而得到的耐火物屑的配合量对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表13。
Figure GDA0002177168210000331
如表13所示,实施例12-1~12-4的含石墨的耐火物是使用变更了耐火物屑、氧化铝原料、碳化硅原料、二氧化硅原料及石墨的配合量的含石墨的耐火物原料、且配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物。这些含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例12-1~12-4的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表13所示,可以确认,将耐火物屑的配合量设为10质量%以上且90质量%以下的范围内的实施例12-1~12-3的含石墨的耐火物具有与仅使用了初始原料的含石墨的耐火物相同程度的耐破裂性和耐熔损性。另一方面,将耐火物屑的配合量设为95.0质量%的实施例12-4的含石墨的耐火物的耐熔损性降低。根据这些结果可以确认,在使用了将使用过的氧化铝/碳化硅/碳质耐火物屑粉碎而得到的耐火物屑作为含石墨的耐火物原料的情况下,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选将耐火物屑的配合量设为10质量%以上且90质量%以下的范围内。
接下来,对于氧化铝/碳质系的含石墨的耐火物中的氧化铝原料和碳化硅原料的配合量对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表14。
Figure GDA0002177168210000351
如表14所示,实施例13-1~13-6的含石墨的耐火物是使用变更了氧化铝原料、碳化硅原料及石墨的配合量的含石墨的耐火物原料、且配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物。这些含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例13-1~13-6的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表14所示,可以确认,将氧化铝原料的配合量设为10质量%以上且95质量%以下的范围内的实施例13-2~13-5的含石墨的耐火物可以较高地保持弯曲强度和破坏能量,而且能够兼顾高耐破裂性和耐熔损性。另一方面,将氧化铝原料的配合量设为6.0质量%的实施例13-1的含石墨的耐火物的弯曲强度和破坏能量降低。将氧化铝原料的配合量设为98质量%的实施例13-6的含石墨的耐火物无法抑制因热剥落导致的裂纹的产生,耐破裂性降低,耐熔损性也降低。根据这些结果可以确认,在使用了氧化铝/碳质系的含石墨的耐火物的情况下,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选将氧化铝原料的配合量设为10质量%以上且95质量%以下的范围内、将碳化硅原料的配合量设为1质量%以上。
接下来,对于二氧化硅/碳质系的含石墨的耐火物中的二氧化硅原料和碳化硅原料的配合量对含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表15。
Figure GDA0002177168210000371
如表15所示,实施例14-1~14-4、比较例14-1的含石墨的耐火物是使用变更了二氧化硅原料、碳化硅原料及石墨的配合量的含石墨的耐火物原料、且配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物。这些含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例14-1~14-4、比较例14-1的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表15所示,可以确认,将二氧化硅原料的配合量设为1质量%以上且50质量%以下的范围内的实施例14-2~14-3的含石墨的耐火物可以较高地保持弯曲强度和破坏能量,而且能够兼顾高耐破裂性和耐熔损性。另一方面,将二氧化硅原料的配合量设为低于1质量%的实施例14-1的含石墨的耐火物中二氧化硅原料的配合量少而石墨的配合量高达99.0质量%,因此耐熔损性大幅降低。将二氧化硅原料的配合量设为98.0质量%的实施例14-4的含石墨的耐火物无法抑制因热剥落导致的裂纹的产生,耐破裂性降低,破坏能量也降低。根据这些结果可以确认,在使用了二氧化硅/碳质系的含石墨的耐火物的情况下,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选将二氧化硅原料的配合量设为1质量%以上且50质量%以下的范围内。
接下来,对于短碳纤维对配合有短碳纤维的含石墨的耐火物的弯曲强度、破坏强度、耐熔损性及耐破裂性造成的影响进行说明。将评价的含石墨的耐火物的制造条件和评价结果示于表16。
Figure GDA0002177168210000391
如表16所示,实施例15-1~15-9的含石墨的耐火物是使用以不同的配合量配合变更了纤维直径和纤维长度的短碳纤维的含石墨的耐火物原料、且配置有将12000根长度为600mm、直径为7μm/根的碳纤维捆扎而成的碳纤维束的含石墨的耐火物。这些含石墨的耐火物的大小与实施例2-1相同,制造方法与表3的说明中记载的方法相同。测定了实施例15-1~15-9的含石墨的耐火物的弯曲强度、破坏能量、耐熔损性及耐破裂性。
如表16所示,额外配合有短碳纤维、且其含量相对于含石墨的耐火物原料为0.10质量%以上且10质量%以下的范围内的15-1~15-4的含石墨的耐火物的弯曲强度和破坏能量高,所述短碳纤维的纤维直径为1μm/根~25μm/根、纤维长度为2μm~1000μm、纤维长度相对于纤维直径的比率为2~40。配合有纤维直径为50μm/根(超过45μm/根)的短碳纤维的实施例15-5的含石墨的耐火物的短碳纤维的纤维直径粗,在成型时发生了起层。因此,实施例15-5的含石墨的耐火物的弯曲强度和破坏能量低于实施例15-1~15-4的含石墨的耐火物。
配合有纤维长度为2000μm(2mm)(超过1000μm(1mm))的短碳纤维的实施例15-6的含石墨的耐火物中碳纤维与耐火物原料的抱合差,在成型时发生了起层。因此,实施例15-6的含石墨的耐火物的弯曲强度和破坏能量低于实施例15-1~15-4的含石墨的耐火物。
配合有纤维长度相对于纤维直径的比率为1(低于2)的短碳纤维的实施例15-7的含石墨的耐火物中碳纤维与耐火物原料的抱合差,因此,实施例15-7的含石墨的耐火物的弯曲强度和破坏能量低于实施例15-1~15-4的含石墨的耐火物。
以0.05质量%(低于0.10质量%)配合有短碳纤维的实施例15-8的含石墨的耐火物中碳纤维的配合量过少,无法获得短碳纤维带来的抑制裂纹扩展的效果。因此,实施例15-8的含石墨的耐火物的弯曲强度和破坏能量低于实施例15-1~15-4的含石墨的耐火物。
以15质量%(超过10质量%)配合有短碳纤维的实施例15-9的含石墨的耐火物中,碳纤维与耐火物原料完全未抱合,在成型时发生了起层。因此,实施例15-9的含石墨的耐火物的弯曲强度和破坏能量低于实施例15-1~15-4的含石墨的耐火物。
根据这些结果可以确认,为了提高含石墨的耐火物的弯曲强度和破坏能量,优选额外配合短碳纤维,且其含量相对于含石墨的耐火物原料为0.10质量%以上且10质量%以下的范围内,所述短碳纤维的纤维直径为1μm/根~25μm/根、纤维长度为2μm~1000μm、纤维长度与纤维直径的比率为2~40。

Claims (23)

1.一种含石墨的耐火物,其是石墨的含量为1质量%以上且80质量%以下的范围内的含石墨的耐火物,其中,
在内部配置长度为100mm以上的碳纤维束,
所述碳纤维束通过在1000根以上且300000根以下的范围内捆扎碳纤维、且端面形成为扁平状,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内,
所述碳纤维束的端面的长边方向与所述含石墨的耐火物的成型面的角度被配置成45°以上且135°以下。
2.根据权利要求1所述的含石墨的耐火物,其中,在1000根以上且60000根以下的范围内捆扎所述碳纤维。
3.根据权利要求1或2所述的含石墨的耐火物,其中,所述含石墨的耐火物包含氧化镁原料,且其含量为20质量%以上且99质量%以下的范围内。
4.根据权利要求1或2所述的含石墨的耐火物,其中,所述含石墨的耐火物包含氧化铝原料,且其含量为10质量%以上且95质量%以下的范围内,而且包含1质量%以上的碳化硅原料。
5.根据权利要求4所述的含石墨的耐火物,其中,所述含石墨的耐火物还包含二氧化硅原料,且其含量为1质量%以上且50质量%以下的范围内。
6.根据权利要求1或2所述的含石墨的耐火物,其中,所述含石墨的耐火物包含将使用过的耐火物粉碎而得到的耐火物屑,且其含量为10质量%以上且90质量%以下的范围内。
7.根据权利要求1或2所述的含石墨的耐火物,其中,使用选自酚醛树脂、氧化铝溶胶、硅溶胶、沥青及焦油中的1种以上粘接剂来粘接所述碳纤维束。
8.根据权利要求1或2所述的含石墨的耐火物,其中,使用选自酚醛树脂、环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化铝溶胶、硅溶胶、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶、氧化钇溶胶、沥青、焦油及淀粉糊中的1种以上粘接剂来粘接所述碳纤维束。
9.根据权利要求1或2所述的含石墨的耐火物,所述含石墨的耐火物还额外包含短碳纤维,且其含量相对于所述含石墨的耐火物为0.10质量%以上且10质量%以下的范围内,所述短碳纤维的纤维直径为1μm/根以上且45μm/根以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)为2以上且1000以下。
10.根据权利要求1或2所述的含石墨的耐火物,其中,多个碳纤维束沿着含石墨的耐火物的长边方向配置于含石墨的耐火物的内部。
11.一种含石墨的耐火物的制造方法,所述含石墨的耐火物在1质量%以上且80质量%以下的范围内含有石墨,且在内部配置有碳纤维束,该方法具有如下工序:
成束工序,将碳纤维捆扎而形成所述碳纤维束;
配合工序,在耐火物原料中配合石墨而制成含石墨的耐火物原料;
成型工序,将配置有所述碳纤维束的所述含石墨的耐火物原料成型而制成成型体;以及
干燥工序,对所述成型体进行干燥,
其中,
在所述成束工序中,在1000根以上且300000根以下的范围内、并使端面为扁平状地捆扎所述碳纤维,形成长度100mm以上的碳纤维束,所述碳纤维的纤维直径为1μm/根以上且45μm/根以下的范围内,
在所述成型工序中,所述碳纤维束的端面的长边方向与所述含石墨的耐火物的成型面的角度被配置成45°以上且135°以下。
12.根据权利要求11所述的含石墨的耐火物的制造方法,其中,
在所述成束工序中,在1000根以上且60000根以下的范围内捆扎所述碳纤维。
13.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化镁原料,
在所述配合工序中,在20质量%以上且99质量%以下的范围内配合所述氧化镁原料。
14.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化铝原料及碳化硅原料,
在所述配合工序中,在10质量%以上且95质量%以下的范围内配合所述氧化铝原料,
配合1质量%以上的所述碳化硅原料。
15.根据权利要求14所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料为氧化铝原料、碳化硅原料及二氧化硅原料,
在所述配合工序中,在10质量%以上且95质量%以下的范围内配合氧化铝原料,
配合1质量%以上的所述碳化硅原料,
在1质量%以上且50质量%以下的范围内配合所述二氧化硅原料。
16.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
所述耐火物原料是将使用过的耐火物粉碎而得到的耐火物屑,
在所述配合工序中,在10质量%以上且90质量%以下的范围内配合所述耐火物屑。
17.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
在所述成束工序中,使用选自酚醛树脂、氧化铝溶胶、硅溶胶、沥青及焦油中的1种以上粘接剂来粘接所述碳纤维。
18.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
在所述成束工序中,使用选自酚醛树脂、环氧树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂、聚氨酯、热固性聚酰亚胺、氧化铝溶胶、硅溶胶、氧化锆溶胶、氧化铬溶胶、二氧化钛溶胶、氧化镁溶胶、氧化钙溶胶、氧化钇溶胶、沥青、焦油及淀粉糊中的1种以上粘接剂来粘接所述碳纤维。
19.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
在所述成型工序之前,还具有如下工序:
混炼工序,对所述含石墨的耐火物原料进行混炼;以及
填充工序,在将所述含石墨的耐火物原料成型的模框中填充经混炼的含石墨的耐火物原料和所述碳纤维束。
20.根据权利要求19所述的含石墨的耐火物的制造方法,其中,
在所述填充工序中,重复进行在相对于所述模框的容积填充了5容积%以上的所述含石墨的耐火物原料后以相互间隔距离为3mm以上排列配置所述碳纤维束的操作,在所述模框中填充所述含石墨的耐火物原料和所述碳纤维束。
21.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
在所述成型工序之前,还具有如下工序:
混炼工序,对所述含石墨的耐火物原料进行混炼;以及
填充工序,在将所述含石墨的耐火物原料成型的成型容器中填充经混炼的含石墨的耐火物原料和所述碳纤维束,
在所述成型工序中,通过压力介质对所述成型容器施加压力而成型为成型体。
22.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,
在所述配合工序中,相对于所述含石墨的耐火物原料,额外在0.10质量%以上且10质量%以下的范围内配合短碳纤维,所述短碳纤维的纤维直径为1μm/根以上且45μm/根以下,纤维长度为1mm以下,纤维长度相对于纤维直径的比率(纤维长度/纤维直径)为2以上且1000以下的范围内。
23.根据权利要求11或12所述的含石墨的耐火物的制造方法,其中,多个碳纤维束沿着含石墨的耐火物的长边方向配置于含石墨的耐火物的内部。
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WO2018155118A1 (ja) * 2017-02-24 2018-08-30 Jfeスチール株式会社 黒鉛含有耐火物および黒鉛含有耐火物の製造方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5177039A (en) * 1990-12-06 1993-01-05 Corning Incorporated Method for making ceramic matrix composites
US5389716A (en) * 1992-06-26 1995-02-14 Georgia-Pacific Resins, Inc. Fire resistant cured binder for fibrous mats
US5418063A (en) * 1989-01-18 1995-05-23 Loral Vought Systems Corporation Carbon-carbon composite and method of making
JPH07206535A (ja) * 1993-12-29 1995-08-08 Osaka Gas Co Ltd 繊維補強耐火構造物およびその製造方法
CN102459722A (zh) * 2009-06-10 2012-05-16 三菱丽阳株式会社 碳纤维用丙烯腈溶胀丝、前驱体纤维束、耐火化纤维束、碳纤维束以及它们的制造方法
CN102858712A (zh) * 2010-03-31 2013-01-02 黑崎播磨株式会社 含厚鳞状石墨耐火物

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05508885A (ja) 1990-06-29 1993-12-09 フレックスリン サービシズ リミテッド 強化複合材の製造方法及びこの方法に用いるためのフィラメント材料
JP3639635B2 (ja) * 1995-03-28 2005-04-20 新日本製鐵株式会社 マグネシア−カーボン質耐火れんがの製造方法
DE19711829C1 (de) * 1997-03-21 1998-09-03 Daimler Benz Ag Verfahren zur Herstellung einer faserverstärkten Verbundkeramik
JP4452030B2 (ja) * 2002-04-03 2010-04-21 新日本製鐵株式会社 無機繊維からなる棒状成形体で補強した耐火物とその製造方法
US7297368B2 (en) 2003-04-15 2007-11-20 Ultramet Method of making carbon fiber-carbon matrix reinforced ceramic composites
JP4388412B2 (ja) 2004-05-07 2009-12-24 新日本製鐵株式会社 機械的強度および耐スポール性に優れる耐火物
JP4731271B2 (ja) 2005-10-12 2011-07-20 新日本製鐵株式会社 繊維強化耐火物
RU2337083C2 (ru) 2006-06-07 2008-10-27 Общество с ограниченной ответственностью "Научно-производственная фирма "Кераком" (ООО "НПФ "Кераком") Способ получения волокнисто-армированного углерод-карбидокремниевого композиционного материала
US20090291278A1 (en) * 2006-08-18 2009-11-26 Kazumasa Kawabe Multiaxially reinforced laminated moldings and process for production thereof
EP2080781A4 (en) * 2006-11-09 2014-06-11 Teijin Chemicals Ltd COMPOSITE MATERIAL AND PROCESS FOR PRODUCING THE SAME
JP5944619B2 (ja) * 2010-02-18 2016-07-05 日立化成株式会社 炭素繊維複合材、及びこの炭素繊維複合材を用いたブレーキ用部材、半導体用構造部材、耐熱性パネル、ヒートシンク
JP5668614B2 (ja) * 2011-06-17 2015-02-12 Jfeスチール株式会社 使用済みマグネシアカーボンレンガの再利用方法およびマグネシアカーボンレンガの製造方法
US9821371B2 (en) 2013-03-21 2017-11-21 Krosakiharima Corporation Refractory material and casting nozzle
WO2018155118A1 (ja) * 2017-02-24 2018-08-30 Jfeスチール株式会社 黒鉛含有耐火物および黒鉛含有耐火物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5418063A (en) * 1989-01-18 1995-05-23 Loral Vought Systems Corporation Carbon-carbon composite and method of making
US5177039A (en) * 1990-12-06 1993-01-05 Corning Incorporated Method for making ceramic matrix composites
US5389716A (en) * 1992-06-26 1995-02-14 Georgia-Pacific Resins, Inc. Fire resistant cured binder for fibrous mats
JPH07206535A (ja) * 1993-12-29 1995-08-08 Osaka Gas Co Ltd 繊維補強耐火構造物およびその製造方法
CN102459722A (zh) * 2009-06-10 2012-05-16 三菱丽阳株式会社 碳纤维用丙烯腈溶胀丝、前驱体纤维束、耐火化纤维束、碳纤维束以及它们的制造方法
CN102858712A (zh) * 2010-03-31 2013-01-02 黑崎播磨株式会社 含厚鳞状石墨耐火物

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